A solid state and theoretical study of the solvent effects controlling the mono- and di-lithiation of aromatic primary amines

D R Armstrong; S C Ball; D Barr; W Clegg; D J Linton; L C Kerr; D Moncrieff; P R Raithby; R J Singer; R Snaith; D Stalke; A E H Wheatley; D S Wright

doi:10.1039/b107970k

A solid state and theoretical study of the solvent effects controlling the mono- and di-lithiation of aromatic primary amines

D R Armstrong, S C Ball, D Barr, W Clegg, D J Linton, L C Kerr, D Moncrieff, P R Raithby, R J Singer, R Snaith, D Stalke, A E H Wheatley, D S Wright

Department of Chemistry

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1 Citation (SciVal)

Abstract

Reaction of 1-naphthylamine, 4-tritylaniline or 4-methylaniline with two equivalents of (BuLi)-Li-n in Et2O or thf affords rare geminal N,N-dilithiates of general formula (L)(n).((LiNAr)-N-2)(10) (L = Et2O, n = 6, Ar = 1-C10H7 1, C6H4-4-CPh3 2; L = thf, n = 10, Ar = C6H4-4-Me 3). X-Ray crystal structure analyses reveal that the core (Li14N10)(6-) frameworks consist of two fused rhombic dodecahedra. Ab initio M. O. calculations on the mono- and di-lithiation of 1-naphthylamine and 4-methylaniline suggest that the selectivity with which polymetallation occurs is solvent dependent and so help to rationalise the experimentally observed structures.

Original language	English
Pages (from-to)	2505-2511
Number of pages	7
Journal	Journal of the Chemical Society: Dalton Transactions
Issue number	12
DOIs	https://doi.org/10.1039/b107970k
Publication status	Published - 2002

Keywords

reactivity
amide ladder structures
tetrahydrofuran
chemistry
ray crystal-structure
basis sets
cage molecule
ring-stacking
lithium anilide
tmeda = me2nch2ch2nme2

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Armstrong, D. R., Ball, S. C., Barr, D., Clegg, W., Linton, D. J., Kerr, L. C., Moncrieff, D., Raithby, P. R., Singer, R. J., Snaith, R., Stalke, D., Wheatley, A. E. H., & Wright, D. S. (2002). A solid state and theoretical study of the solvent effects controlling the mono- and di-lithiation of aromatic primary amines. Journal of the Chemical Society: Dalton Transactions, (12), 2505-2511. https://doi.org/10.1039/b107970k

Armstrong, DR, Ball, SC, Barr, D, Clegg, W, Linton, DJ, Kerr, LC, Moncrieff, D, Raithby, PR, Singer, RJ, Snaith, R, Stalke, D, Wheatley, AEH & Wright, DS 2002, 'A solid state and theoretical study of the solvent effects controlling the mono- and di-lithiation of aromatic primary amines', Journal of the Chemical Society: Dalton Transactions, no. 12, pp. 2505-2511. https://doi.org/10.1039/b107970k

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title = "A solid state and theoretical study of the solvent effects controlling the mono- and di-lithiation of aromatic primary amines",

abstract = "Reaction of 1-naphthylamine, 4-tritylaniline or 4-methylaniline with two equivalents of (BuLi)-Li-n in Et2O or thf affords rare geminal N,N-dilithiates of general formula (L)(n).((LiNAr)-N-2)(10) (L = Et2O, n = 6, Ar = 1-C10H7 1, C6H4-4-CPh3 2; L = thf, n = 10, Ar = C6H4-4-Me 3). X-Ray crystal structure analyses reveal that the core (Li14N10)(6-) frameworks consist of two fused rhombic dodecahedra. Ab initio M. O. calculations on the mono- and di-lithiation of 1-naphthylamine and 4-methylaniline suggest that the selectivity with which polymetallation occurs is solvent dependent and so help to rationalise the experimentally observed structures.",

keywords = "reactivity, amide ladder structures, tetrahydrofuran, chemistry, ray crystal-structure, basis sets, cage molecule, ring-stacking, lithium anilide, tmeda = me2nch2ch2nme2",

author = "Armstrong, {D R} and Ball, {S C} and D Barr and W Clegg and Linton, {D J} and Kerr, {L C} and D Moncrieff and Raithby, {P R} and Singer, {R J} and R Snaith and D Stalke and Wheatley, {A E H} and Wright, {D S}",

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doi = "10.1039/b107970k",

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T1 - A solid state and theoretical study of the solvent effects controlling the mono- and di-lithiation of aromatic primary amines

AU - Armstrong, D R

AU - Ball, S C

AU - Barr, D

AU - Clegg, W

AU - Linton, D J

AU - Kerr, L C

AU - Moncrieff, D

AU - Raithby, P R

AU - Singer, R J

AU - Snaith, R

AU - Stalke, D

AU - Wheatley, A E H

AU - Wright, D S

N1 - ID number: ISI:000176051000018

PY - 2002

Y1 - 2002

N2 - Reaction of 1-naphthylamine, 4-tritylaniline or 4-methylaniline with two equivalents of (BuLi)-Li-n in Et2O or thf affords rare geminal N,N-dilithiates of general formula (L)(n).((LiNAr)-N-2)(10) (L = Et2O, n = 6, Ar = 1-C10H7 1, C6H4-4-CPh3 2; L = thf, n = 10, Ar = C6H4-4-Me 3). X-Ray crystal structure analyses reveal that the core (Li14N10)(6-) frameworks consist of two fused rhombic dodecahedra. Ab initio M. O. calculations on the mono- and di-lithiation of 1-naphthylamine and 4-methylaniline suggest that the selectivity with which polymetallation occurs is solvent dependent and so help to rationalise the experimentally observed structures.

AB - Reaction of 1-naphthylamine, 4-tritylaniline or 4-methylaniline with two equivalents of (BuLi)-Li-n in Et2O or thf affords rare geminal N,N-dilithiates of general formula (L)(n).((LiNAr)-N-2)(10) (L = Et2O, n = 6, Ar = 1-C10H7 1, C6H4-4-CPh3 2; L = thf, n = 10, Ar = C6H4-4-Me 3). X-Ray crystal structure analyses reveal that the core (Li14N10)(6-) frameworks consist of two fused rhombic dodecahedra. Ab initio M. O. calculations on the mono- and di-lithiation of 1-naphthylamine and 4-methylaniline suggest that the selectivity with which polymetallation occurs is solvent dependent and so help to rationalise the experimentally observed structures.

KW - reactivity

KW - amide ladder structures

KW - tetrahydrofuran

KW - chemistry

KW - ray crystal-structure

KW - basis sets

KW - cage molecule

KW - ring-stacking

KW - lithium anilide

KW - tmeda = me2nch2ch2nme2

U2 - 10.1039/b107970k

DO - 10.1039/b107970k

M3 - Article

SP - 2505

EP - 2511

JO - Dalton Transactions

JF - Dalton Transactions

SN - 1477-9226

IS - 12

ER -

A solid state and theoretical study of the solvent effects controlling the mono- and di-lithiation of aromatic primary amines

Abstract

Keywords

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